Treatment of textile materials



Patented Sept. 4, 1934 UNITED STATES- PATENT o FmE TREATMENT OF TEXTILE MATERIAL George Holland Ellis, Spondon, near Derby, England, assignor to Oelanese Corporation of America, a corporation of Delaware No Drawing. Application March 26, 1930, Serial No. 439,264. In Great Britain April 29, 1929 17 Claims.

This invention relates to the production of col oured pattern effects onfabrics or other textile materials.

In the colouration of textile materials, particularly in the case of fabrics, it is frequently required to produce white or coloured pattern effects on a coloured ground, and such effects are commonly produced by dyeing or otherwise colcuring the fabric and then removing or changing the colour of selected portions by the application of the so-called discharging agents which may destroy the colouring matter or may convert it into an uncoloured or differently coloured compound or into a form in which it is easily removed from the fabric by washing. Thus certain colouring matters can be discharged by the application of reducing'agents, certain others by application of oxidizing agents, while some can be discharged by either oxidizing or reducing agents. If the discharging agent is mixed with a colouring matter which is not, destroyed thereby but which has affinity for the fabric or other material to be treated it is possible not only to remove the ground colour in selected places but to substitute another colour therefor; in this manner the so-called coloured discharges may be obtained. I l

The production of such white and coloured discharge efiects on materials made of or containing cellulose acetate or other organic acid esters of cellulose or cellulose ethers has been attended with some difficulty but very good discharge effects can be produced on such materials by the chlorate discharge process described in British Patent No. 312,655, or by the use of chromates U. S. Patent No. 1,905,346.

Valuable white or coloured discharge effects can also be obtained on materials made of or containing cellulose acetate or, other organic acid esters or ethers of cellulose by the processes described in United States Patent No. 1,922,927. According to this specification discharge effects 1 are obtained by applying to the material a diazotizable amine or colouringjmatter, then printing a discharging agent which may be an oxidizing or a reducing agent, and thereafter diazot'lzing and combining with a coupling component which may 1 be applied simultaneously with or separately from the diazotizable compound. v

According to the present invention in the production of white or coloured discharge effects on textile materials, .the material is, impregnated with a. substance having an acid reaction prior to the application of the discharging agent.

The employment of a substance of acid reaction in this manner greatly facilitates the action of the discharging agent, particularly when operating on materials made of or containing cellulose acetate or other cellulose esters, or cellulose vention is not only applicable in those cases where discharge of a colouring matter already present in the material is to be effected but is equally applicable where a diazotizable compound is to be discharged locally, prior to diazotization and development, in the manner described in the aforesaid United States Patent No. 1,922,927.

As substances of acid reaction which may be employed according to the invention may be mentioned organic acids, particularly organic carboxylic acids, preferably such as are only volatile with difficulty, for example oxalic acid, tartaric acid, or citric acid. Other acids which may be used are for example salicylic acid, benzoic acid, a naphthoic acid, and sulphom'e acids such as those of benzene, phenol, naphthalene, or the naphthols. The invention is not however limited to the use of organic acids since other substances having an acidic reaction, for instance acid salts or salts which have an acid reaction,

for example aluminium sulphate or zinc sulphate,

may be employed. Care should be taken that the acid substance is not of such nature or is not used under such conditions as would lead to damage to the textile material under treatment.

The substances of acid reaction may be applied to dyed materials in anyconvenient manner, for example by passing the materials through a solution thereof in water or by padding them with such a solution. The latter method is particularly convenient in the case of woven fabrics. After the impregnation with the acid substance the materials are preferably dried prior to the application of the discharging agent.

As discharging agents may be used any of those commonly used in the art of textile printing, for example reducing agents such as hydrosulphites or formaldehyde sulphoxylates, especially sodium formaldehyde sulphoxylates, or oxidizing agents sfiich as chlorates or chromates. They will in general be applied to the textile materials in admixture with thickening agents designed to give them the physical properties necessary in a preparation which is to be applied to a fabric by printing or other mode of local application. Further the discharging preparation may contain catalytic or other substances which assist the discharging action on the dyed material; thus a reducing discharge preparation may contain anthraquinone, and an oxidizing discharge preparation may contain an acidic substance and/or oxidation. catalysts such as salts of iron, prussiates, or salts of vanadium. When it is required to produce discharge effects upon materials made of or containing cellulose esters or ethersraccording to the *process of the invention the action of the discharging preparation may frequently be intensified by incorporating therein a swelling agentfor the said cellulose derivative, for example a sulphocyanide or alcohol, e. g. in the form of methylated spirit.

Coloured discharges can be produced according to the invention by incorporating in the discharge preparations colouring matters which are not destroyed thereby under the working conditions and which have aflinity for or can be fixed on the textile material under treatment. Vat dyestufis, certain basic dyestuffs such as methylene blue or rhodamine 6 G extra, and certain mordant dyestuffs are particularly suitable for incorporation in reducing discharges. For use in oxidizing discharges may be mentioned the resistant colouring matters referred to in British Patent No. 312,655, for example colouring matters of the mineral pigment type such as chrome yellow,

' lemon chrome yellow, Guignets green, and vermilion, organic dyestuffs of the pigment type (insoluble in water, but soluble in oils, fats, soaps or the like) e. g. resistant vat dyes of the anthraquinone series or the following insoluble azo dyes: innitraniline naphthol A S, p-nitraniline-*fl-naphthol or naphthol A S, and p-nitro-otoluidine-nS-nziphthol or naphthol A S, certain basic dyestuifs for example methylene blue and rhodamine 6 G extra. i

For colouring oxidizing discharges intended for application to materials made of or containing cellulose esters or ethers, many of the dyestuifs normally employed for colouring such materials are very suitable. For example nitrodiarylamine colouring matters and aminoanthraquinone colouring matters can. be used very successfully.

Care should be exercised however in the choice of dyestuifs of the lat-aminoanthraquinone series since some members of this class having a substituent, particularly hydroxyl or amino, in the para position to the a-amino group are insufliciently resistant to the action of oxidizing discharge preparations.

Other colouring matters which have been found useful, particularly for incorporation in oxidizing discharge preparations, are the acidyl aminoanthraquinones whether simple acidylamino compounds or containing in addition to acidylamino groups other substituent groups or atoms such as hydroxyl groups, alkoxyl groups, and halogen atoms. Of this group of colouring matters the aliphatic acidyl aminoanthraquinones are'of especial interest for use in colouring oxidizing discharge preparations for application to cellulose ester or ether materials owing to their good a ffinity for such materials; the following are examples of such aliphatic acidyl aminoan- I thraquinones and the 'colourations yielded by them when applied to cellulose ester or ether materials:- I

1-acetylamlno-anthragulnone Yellow l propionylamino-ant raquinone Yellow 1 aeetylamino 2 methyl anthra- 0 quinone Yellow (less green) 1 acetylamin'o 4 hydroxy anthraquinone Golden orange 1 gropionylamino 4 methoxy an- I t rnqulnone Golden yellow 1 4 (ii (prcpionylamino) anthra quinone Red 1 methylamino 4 acetylamlno-anthraquinoneflh Reddish violet 1 4 di (acetyletliylamino) anthraquinone Red 1 5 di (acetylamino) 4 :8 dihydroxy anthraquinone Red 1 propionylmethylamino 4 5 dihydroxy-antliraquinone Red 1 5 di (acetylmethylamino) 5 dihydroxy-anthraquinone Violet 2-propionylamino-anthraquinone Pale greenish yellow The above aliphatic acidylaminoanthraqumones may be prepared by treating the corresponding aminoanthraquinone or aminoanthraquinone derivative with the acid anhydride, acetic or propionic, in acetic acid solution.

The dyestuifs in the coloured discharge preparations may if desired or requisite be applied in conjunction with a fixing agent or agents, for example with albumen in the case of pigment dyestuffs and with mordants in the case of mordant or basic dyestuffs. Vat dyestuffs may be applied in the form of the esters of their leuco compounds.

The application of the discharge preparations to the dyed material, afterincorporating a substance of acid reaction therein, may be effected in any desired manner, for. example by machine or hand-block printing, stencilling, spraying or the like.

As previously indicated the presence of the substance of acid reaction in the dyed material greatly facilitates the action of the discharging agent, so much so, that the discharging action frequently takes place on simply drying the material after applying the agent and without the subsequent ageing or steaming operation commonly practised in the art. In the production of coloured discharges however, steaming is often desirable to fix satisfactorily the colouring matter on the discharged portions of the materials. Where such is the case and the said colouring matter is .insufliciently resistant to the combined action of steam, discharging agent, and an acid, the last mentioned may be neutralized prior to steaming, for example by treatment with gaseous ammonia or with a dilute solution of ammonia, soda ash, or other alkali. Especially useful results are obtained as previously indicated when the new process is applied to the treatment of textile materials made of or containing cellulose acetate or other cellulose esters, or cellulose ethers. For example, valuable coloured discharge elfects in great variety can readily be produced upon such L,

materials coloured with dischargeable dyestuffs of the gallocyanine series or basic dyestuffs of the diaryl-methane, triarylmethane, thiazine, oxazine, azine, or xanthene series. For instance, material dyed with one or more of the aforementioned colouring matters may be impregnated with a substance having an acid reaction and an oxidizing discharge preparation containing a colouring matter of the nitrodiarylamine or aminoanthraquinone series applied by printing or other mode of local application. Discharge of the ground colouration may be effected without steaming, for example by .drying the printed fabric by means of warm or hot air or heated surfaces such as cylinders, but, in order to fix prop- Water erLv the colouring matter on the discharged portions of the material, the latter may be subsequently steamed after treatment with an alkali, for example, gaseous ammonia or dilute aqueous The invention is applicable to the production ofdischargeefiects ontextilematerialsofall kinds, for example materials made of or containing cotton, silk, or artificial silk whether of the regenerated cellulose type or of the type made from cellulose esters, for example cellulose acetate, formate, propionate, or butyrate, or the products obtained by the treatment of cellulose with esterifying agents (e. g. the product known as immunized cotton p-toluene-sulphochloride) or made from cellulose ethers, for instance methyl, ethyl, or benzyl cellulose or the corresponding condensation prodnets of cellulose and yo ls or other polyhydric alcohols. Mixed materials made from two or more types of textile filaments, threads or yarns mayalsobetreatedinaccordancewiththeinven- The following examples show the best way known to us for carrying the invention into effect but are not intended to limit it in any way.

Example 1 printed with a discharge paste composed as follows:-- I

Grams Gum'arabic 1: 450 Almninium sulphate 1:1 190 Sodium chlorate... 90 Potasium ferricyanide The printed fabric is dried hard, either in a hotchamberoronsteamheateddrumaafter whichitiswashedfreefrom-acidinwaterand finallysoapedlightly. Awhitepatternonadeep blue-violet ground is thus obtained.

Example-2 A fabric woven from cellulose acetate yarns is dyed in a dyebath of volume ratio :1 with 05% of its weight of benzene-azo-l-phenyl-a-methyb S-pyrazblone, the dyestuif being dispersed before adding to the dyebath by heating with four times its weight of After dyeing for 1 hours at C. the material is andthenpadded'ma5% solution of citric acid. Squeezing to leave its own weight of liquor in the fabric, and Itisthenprintedwith thepastegiveninExample 1, dried and suitably steamed for 2 minutes at100C.aIter whichitisrinsedwellandsoaped :3v retainitsownweightofpadliquonanddried.

The acid padded fabric is printed with the following discharge paste:

. Granis' -Gmn ambic 1' 580 80 Zinc oxide 7 .50 methylated spirit 100 Anthraquinone 10% paste 70 Formosul 150 The printed fabric is dried and suitably steamed either in the rapid ager" or in the cottage steamer, after which it is rinsed and soaped lightly. A white pattern on a bright orange ground'is ob- Example 4 A woven fabric of cellulose acetate yarns isdyed by known methods with 0.5% of its weight of Q-nitro-il-methoxy-benzene-azodiethylaniline andafterdrying itis p'addedin a 5% solution of benaene-sulphonic' acid, being to retain about its own weight of liquor,

and The padded fabric'is' printed witha' paste composed as follows: Grams Gum arabic 1: 500 Ciba blue 23. powder 50 Anthraquinone 10% paste 60 hydrosulphite 30 Caustic soda 30 Soda ash 30 Water 100 methylated spirit. 50 Formosul 100 thematerlalisdried and suitably steamed'eitherintherapidager or cottage steamerandoxidizedinabathofsodiumdichromateforSminutes'atGO C. Itisflnally rinsed and soap'ed. A blue pattern on a red groundisobtained.

EmpleS A fabric of cellulose acetate yarns isdyedbyak nownmethodwithwtofitsweight of violet P.D."H. (Colour Index No. 893). After dryingitispaddedinasubstanceofanacid character, for instance as described in Example 1,2,3or4,andafterdryingisprintedwitha paste of the following composition:-

armm'intingthefabricisdriedonsteam* heated drums and then neutralized either by gassingwithammoniainasuitable apparatus orpaddinginanaqueous solutionofanalkaline character, until there isno acid reaction, after whichitisdriedandsteamedforlsminutesat 5 lbs. pressure int-he cottage steamer. The

brightredpatternonadeephlue-violetgrmmd isthus obtained. 5

' Sodium chlorate Example 6 A woven fabric composed of cellulose acetate yarns is dyed by a known method with 3% of its weight of crystal violet (Colour Index No. 681) and after dyeing is padded in a substance of an acid nature, for instance as described in Example 1, 2, 3 or 4. The material, after drying, is printed with a printing paste composed as follows:-

Grams Gum arabic l:l l 440 Aluminium sulphate 1:1 190 Water 100 2:4 dinitro diphenylamine 20% w a t e r paste Potassium ferricyanide 1000 After printing the fabric is dried, neutralized with alkali, steamed in the cottage steamer and finished as described in Example 5. A brilliant yellow pattern on a violet ground is thus obtained.

Example 7 After printing the fabric is dried, neutralized with a substance of an alkaline nature as described in Examples 5 and 6, steamed, rinsed and soaped. A bright orange design on a blue ground is obtained.

- Example 8 A fabric composed of silk yarns is dyed by a known method with 3% of its weight of seto-' glaucine (Colour Index No. 658) and after drying is padded in a solution of a substance of an acid character as in Example 7. After the material is printed with a printing paste composed as follows:

Grams Gum arabic 1:1 650 Zinc oxide 50 Water 150 Formosul 150 The printed fabric is dried and suitably steamed either in the rapid ager or in the cottage steamer, after which it is rinsed and soaped lightly. A white pattern on a turquoise blue ground is obtained.

Example 9 A woven fabric composed of cotton yarns is dyed by known methods with 2% of its weight of chlorazol sky blue F. F. (Colour Index No. 618) and after drying is padded in a 2% solution of citric acid, squeezing to leave its own weight of liquor in the fabric, and carefully dried. The acid padded fabric is printed with the following discharge paste:

The printed fabric is dried and suitably steamed either in the rapid ager or in the cottage steamer, after which it is rinsed and soaped lightly. A

white pattern on a bright blue ground is obtained.

What I claim and desire to secure by Letters Patent is:-

1. In the production of discharge effects on textile materials, impregnating the materials with a substantially non-volatile substance having an acid reaction and drying the same prior to the application of the discharging agent.

2. In, the production of discharge effects on textile materials comprising an organic derivative of cellulose, impregnating the materials with a substantially non-volatile organic acid and drying the same prior tothe application of the discharging agent.

3. In the production of discharge effects on textile materials comprising cellulose acetate, impregnating the materials with a substantially non-volatile organic acid and drying the same prior to the application of the discharging agent.

4. In the production of discharge effects on textile materials comprising an organic derivative of cellulose, impregnating the materials with a substantially non-volatile organic acid and drying the same prior to the application of a dis-' charging agent which comprises an oxidizing agent.

5. Process for the production of discharge effects on textile materials, comprising impregnate ing the dyed materials with an aqueous solution of a substantially non-volatile substance having an acid reaction, drying the materials, and locally applying a discharging agent.

6. Process for the production of discharge effects on textile materials comprising an organic derivative of cellulose, comprising impregnating the dyed textile materials with an aqueous solution of a substantially non-volatile substance having an acid reaction, drying the materials, and locally applying a discharging agent.

7. Process for the production of discharge effects on textile materials comprising cellulose acetate, comprising impregnating the dyed textile materials with an aqueous solution of a substantially non-volatile substance having an acid reaction, drying the materials, and locally applying a discharging agent.

8. Process for the production of discharge effects on textile materials comprising an organic derivative of cellulose, comprising impregnating the dyed materials with an aqueous solution of a substantially non-volatile substance having an acid reaction, drying the materials, and locally applying an oxidizing discharge.

9. Process for the production of discharge effects on textile materials comprising cellulose acetate, comprising impregnating the dyed materials with an aqueous solution of a substantially non-volatile substance having an acid reaction, drying the materials, and locally applying an oxidizing discharge.

10. Process for the production of discharge effects on textile materials comprising an organic derivative of cellulose, comprising impregnating the dyed materials with an aqueous solution of a substantially non-volatile organic acid, drying the materials, and locally applying an oxidizing discharge.

11. Process for the production of discharge efiects on textile materials comprising cellulose acetate, comprising impregnating the dyed maerials with an aqueous solution of a substantially non-volatile organic acid, drying the-materials, and locally applying an oxidizing discharge.

12. Process for the production of discharge efiects on textile materials comprising an organic derivative of cellulose, comprising impregnating the dyed textile materials with an aqueous solution of a substantially non-volatile organic acid,

drying the materials, and locally applying an oxidizing discharge composition containing resistant difficulty soluble coloring matters selected from the group consisting of the amino-anthra--v quinone, aliphatic acidyl-aminoanthraquinone, or nitro-diarylamine series.

13. Process for the production of discharge effects on textile materials comprising cellulose acetate, comprising impregnating the dyed textile materials with an aqueous solution of a sub-. stantially non-volatile organic acid, drying the materials, and locally applying an oxidizing discharge composition containing resistant difficultly soluble coloring matters selected from the group consisting of amino-anthraquinone, a1i-' phatic acidyl-amino-anthraquinone, or nitro-diarylamine series. v

14. Process for the production of discharge effects on textile materials, comprising impregnating the dyed materials with an aqueous solution of a substantially non-volatile substance having an acid reaction, drying the materials, locally ap plying a discharging agent containing a coloring matter resistant thereto, neutralizing the substance having an acid reaction, and then subjecting the materials to a steaming operation to fix the coloring matter.

15. Process for the production of discharge e1.- fects on textile materials comprising an organicv derivative of cellulose, comprising impregnating the dyed materials with an aqueous solution of -a substantially non-volatile substance having an acid reaction, drying the materials, locally applying a discharging agent containing a coloring matter resistant thereto, neutralizing the substance having an acid reaction, and then subjecting the materials to a steaming operation to fix the coloring matter.

16. Process for the production of discharge ef- I fects on textile materials comprising cellulose acetate, comprising impregnating the dyed materials with an aqueous solution of a substantially non-volatile substance having an acid re action, drying the materials, locally applying discharging agent containing a coloring matt resistant thereto, neutralizing the substance ha ing an acid reaction, and then subjecting the materials to a steaming operation to fix the.

coloring matter. 1

1'7. Process for the production of discharge effects on textile materials comprising an organic derivative of cellulose, comprising impregnating the dyed materials with an aqueoussolution of a substantially non-volatile organic acid, drying -the materials, locally applying a discharging GEORGE HOLLAND ELLIS.

CERTIFICATE or connection.

Puem No. 1.972.137.

September 4, I 1934. I

GEORGE HOLLAND ELLIS.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Page 2, line 90. for

' 'l:5-'di" read l:4-d i; and that the said Letters Patent should be read with this correction therein that the same may conform Patent Office.

to the record of the case in the Signed and sealed this 25in day of September, 5.1); 1934.

Leslie Frazer Acting Commissioner of Patents.

derivative of cellulose, comprising impregnating the dyed materials with an aqueous solution of a substantially non-volatile organic acid, drying the materials, and locally applying an oxidizing discharge.

11. Process for the production of discharge efiects on textile materials comprising cellulose acetate, comprising impregnating the dyed maerials with an aqueous solution of a substantially non-volatile organic acid, drying the-materials, and locally applying an oxidizing discharge.

12. Process for the production of discharge efiects on textile materials comprising an organic derivative of cellulose, comprising impregnating the dyed textile materials with an aqueous solution of a substantially non-volatile organic acid,

drying the materials, and locally applying an oxidizing discharge composition containing resistant difficulty soluble coloring matters selected from the group consisting of the amino-anthra--v quinone, aliphatic acidyl-aminoanthraquinone, or nitro-diarylamine series.

13. Process for the production of discharge effects on textile materials comprising cellulose acetate, comprising impregnating the dyed textile materials with an aqueous solution of a sub-. stantially non-volatile organic acid, drying the materials, and locally applying an oxidizing discharge composition containing resistant difficultly soluble coloring matters selected from the group consisting of amino-anthraquinone, a1i-' phatic acidyl-amino-anthraquinone, or nitro-diarylamine series. v

14. Process for the production of discharge effects on textile materials, comprising impregnating the dyed materials with an aqueous solution of a substantially non-volatile substance having an acid reaction, drying the materials, locally ap plying a discharging agent containing a coloring matter resistant thereto, neutralizing the substance having an acid reaction, and then subjecting the materials to a steaming operation to fix the coloring matter.

15. Process for the production of discharge e1.- fects on textile materials comprising an organicv derivative of cellulose, comprising impregnating the dyed materials with an aqueous solution of -a substantially non-volatile substance having an acid reaction, drying the materials, locally applying a discharging agent containing a coloring matter resistant thereto, neutralizing the substance having an acid reaction, and then subjecting the materials to a steaming operation to fix the coloring matter.

16. Process for the production of discharge ef- I fects on textile materials comprising cellulose acetate, comprising impregnating the dyed materials with an aqueous solution of a substantially non-volatile substance having an acid re action, drying the materials, locally applying discharging agent containing a coloring matt resistant thereto, neutralizing the substance ha ing an acid reaction, and then subjecting the materials to a steaming operation to fix the.

coloring matter. 1

1'7. Process for the production of discharge effects on textile materials comprising an organic derivative of cellulose, comprising impregnating the dyed materials with an aqueoussolution of a substantially non-volatile organic acid, drying -the materials, locally applying a discharging GEORGE HOLLAND ELLIS.

CERTIFICATE or connection.

Puem No. 1.972.137.

September 4, I 1934. I

GEORGE HOLLAND ELLIS.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Page 2, line 90. for

' 'l:5-'di" read l:4-d i; and that the said Letters Patent should be read with this correction therein that the same may conform Patent Office.

to the record of the case in the Signed and sealed this 25in day of September, 5.1); 1934.

Leslie Frazer Acting Commissioner of Patents. 

